Chloroaniline salts of alpha, alpha-dichloro-propionic acid



United States Patent CHLOROANILINE SALTS OF a,a-DICHLORO- PROPIONIC ACIDCharles T. Pumpelly, Midland, Mich., assignor to The Dow ChemicalCompany, Midland, Mich., a corporation of Delaware No Drawing.Application December 29, 1955 Serial No. 556,081

3 Claims. (Cl. 260-501) This invention is concerned with themonochloroaniline salts of u,u-dichloropropionic acid having thefollowing formula 0113-0 on-ii-o-rrm-Q These new compounds arecrystalline solid materials which are somewhat soluble in many organicsolvents and of very high solubility in water. These compounds areactive as herbicides and are adapted to be employed for the controlofthe growth and killing of Weeds and for the sterilization of soil withregard to plant growth.

The new compounds may be prepared by reacting a,a-dichloropropionic acidwith a monochloroaniline. In carrying out the reaction, the reactantsmay be added portionwise one to the other with stirring. Inanalternative method, the reagents may be contacted in an organic solventsuch as ether or benzene. Good results are obtained when operating attemperatures of from 0 to 60 C., and when employing substantiallyequimolecular proportions-of the reactants. The reaction is exothermic,the temperature being controlled by regulating the rate of contactingthe reactants and by external cooling. During the reaction, theamt-dichloropropionic acid monochloroaniline salt separates in thereaction mixture as a crystalline solid. This product may be separatedby filtration.

In a preferred method of operation, one molecular proportion ofa,a-dichloropropionic acid is added slowly portionwise to one molecularproportion of the monochloroaniline dissolved in diethyl ether. Theaddition is carried out with stirring and cooling and at a temperatureof from 0 to 60 C. Following the reaction, the mixture is filtered toseparate the desired salt product.

The following examples illustrate the invention and are not to beconstrued as limiting:

Example 1 A quantity of m,a-dichloropropionic acid (143 grams, 1 mole)was added slowly portionwise to 127 grams (1 mole) of 3-'chloroanilin edissolved in 300 milliliters of diethyl ether. The addition was carriedout with stirring and cooling and at a temperature of C. Duringtheaddition of a,adichloropropionic acid 3- chloroaniline salt separated inthe reaction mixture as a chloroaniline salt as a crystalline solidhaving a mt lecular weight of 280.

Example 3 One mole of a,a-dichloropropionic acid was adde slowlyportionwise to one mole of 4-chloroaniline di: solved in 400 millilitersof diethyl ether. The additio was carried out with stirring and coolingand at a ten perature of from 10 to 20 C. During the additio an0:,a-diCh1OIOPIOPi011lC acid 4-chloroaniline produt separated in thereaction mixture as a crystalline S01i( Following the reaction the saltproduct was separate by filtration and the filtrate evaporated todryness t obtain an additional quantity of product. The a,a-dchloropropionic acid 4-chloroaniline salt was obtained i a yield of 95.5percent and had a melting point t l101l2 C.

The monochloroaniline salts of a, x-dichloropropioni acid are effectiveas plant growth control agents and a1 adapted to be employed for thekilling of plants and th sterilization of soil with regard to plantgrowth. R such use the products may be dispersed on a finely d videdcarrier and employed as dusts. Also, the no products may be employed inoils and as constituen' of aqueous compositions. I

The highly desirable and beneficial results to be 01 tained with thecompounds of the present invention a1 illustrated as follows. Aqueouscompositions containir 0.04 pound of the aniline and 3-chloroanilinesalts a,a-dichloropropionic acid were employed for the COl'ltl't of thegrowth of the germinant seeds and emergir seedlings of pigweed,lambsquarters and wild buckwhea In such operations, the compositionswere applied 1 seed beds as a soil drench and at a rate of about 0.4acre inch of aqueous composition per acre to' supply dosage of fivepounds of one of the salt compounds p1 acre. Immediately prior to theapplications, the set beds had been prepared and seeded with the nameplant species. Other seed beds similarly seeded We] left untreated toserve as checks.

After three weeks, the treated beds were examined to a certain whatcontrol of the growth of seeds and emergii seedlings had been obtained.The examination indicate a 90 percent control of lambsquarters and a 100perce: control of pigweed and wild buckwheat has been 0' tained in thebeds treated with the 3-chloroaniline s: of 0:,oc-diChIOI'OPIOPiOI1iCacid. In the beds treated M the aniline salt of a,u-dichloropropionicacid a zei percent control of the growth of the seeds and. emergiiseedlings of the named plant species was obtained. 1 the time of theobservations, the untreated check be were found to support abundant andvigorously growii crystalline solid. This product was separated byfiltra- Example 2 Equal molar quantities of u,a-dichloropropionic acidand 2-chloroaniline are reacted together as described in Example 1 toobtain an a,oc-dichlorop ropionic acid 3- stands for lambsquarters,pigweed and wild buckwhet I claim: v i

1. A monochloroaniline salt of a,a-dichloropropion acid of the formula2. The 3-chloroaniline salt of a,-dichloropropion acid.

3. The 4-chloroaniline salt of a,a-dichloropropion acid.

References Cited in the file of this patent UNITED STATES PATENTS I2,393,086 Bosquet Ian. 5, '19 2,673,877 Thompson Mar. 30, 19. 2,689,262a Scoles Sept. 14, 19;

1. A MONOCHLOROANILINE SALT OF A,A-DICHLOROPROPIONIC ACID OF THE FORMULA